Simultaneous determination of the heat and the quantity of vapor sorption using a novel microcalorimetric method

In this study, instrumentation for measuring vapor sorption enthalpies and sorption uptakes simultaneously with an isothermal microcalorimeter is introduced. Various pharmaceutical model substances undergoing phase transitions when exposed to humid conditions (25 degrees C), were employed to evaluate the usefulness and sensitivity of the constructed experimental method.

The sample is placed in the sample vessel of a RH cell and the moisture content of the air flow is controlled. From the RH cell the air flow is conducted into a subsequent perfusion cell in which a saturated salt solution has been loaded. The RH cell and perfusion cells are positioned in the sample sides of two twin calorimetric units. Depending on the moisture content in the outlet flow leaving the preceding RH cell, the heat flow signal from the subsequent perfusion cell will vary. By means of blank measurement with identical settings, the rate of water sorption can be calculated and, by integration, the amount of sorbed water is obtained.

Amorphous lactose and cefadroxil undergo recrystallization when the moisture level in the surroundings exceeds the threshold values specific to each compound. During the sorption phase, heat is evolved fairly linearly as a function of consumed moisture, and also after the recrystallization, the heats indicate linear behavior. The heat values for the desorption phase of amorphous lactose and the adsorption of crystalline lactose coincide. With the different anhydrous forms of theophylline, the hydration takes place more rapidly in the metastable form 1, and generally, the process is more energetic in form 1. In all cases, the gravimetric results agree with the water sorption uptakes calculated from the calorimetric data.

The technique introduced offers a rapid and sensitive method to gain new insights into the transitions in which vapors are involved. In addition, different kinds of surfaces with various energetics can now be studied more closely.